US8535398B1 - Chemical complexes comprising glycerine and monoglycerides for thickening purposes - Google Patents
Chemical complexes comprising glycerine and monoglycerides for thickening purposes Download PDFInfo
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- US8535398B1 US8535398B1 US13/467,863 US201213467863A US8535398B1 US 8535398 B1 US8535398 B1 US 8535398B1 US 201213467863 A US201213467863 A US 201213467863A US 8535398 B1 US8535398 B1 US 8535398B1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1826—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms poly-hydroxy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L11/00—Manufacture of firelighters
- C10L11/04—Manufacture of firelighters consisting of combustible material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L7/00—Fuels produced by solidifying fluid fuels
- C10L7/02—Fuels produced by solidifying fluid fuels liquid fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
- C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
Definitions
- the present invention is generally directed to systems and methods for thickening liquids, e.g., hydrophobic liquids, non-aqueous liquids, fuels, etc.
- Various aspects of the present invention generally relate to solid monoglyceride-containing compositions containing an agent that modifies the molecular and microscopic structure, and the dispersal properties of monoglycerides in hydrophobic liquids.
- hydrophobic liquids such as fuels, including hydrocarbon alkane-based odorless mineral spirits, paraffin oil and biofuels, e.g., mono-alkyl esters of medium to long chain (C 8 -C 18 ) fatty acids, that have been thickened or gelled by fatty acid monoglycerides such as glyceryl monostearate and glyceryl monopalmitate, that have been modified with hydrogen-bonded glycerine.
- fuels including hydrocarbon alkane-based odorless mineral spirits, paraffin oil and biofuels, e.g., mono-alkyl esters of medium to long chain (C 8 -C 18 ) fatty acids, that have been thickened or gelled by fatty acid monoglycerides such as glyceryl monostearate and glyceryl monopalmitate, that have been modified with hydrogen-bonded glycerine.
- Mineral spirits are petroleum distillates derived from the light distillate fractions during the crude oil refining process, and are generally composed of six to eleven carbon (C 6 -C 11 )-containing alkane hydrocarbon compounds (though small amounts of other compounds may be present), with the majority of the mass composed of C 9 -C 11 alkanes.
- Mineral spirits are commonly used as a paint thinner and mild solvent. In industry, mineral spirits are used in conjunction with cutting oil, and for cleaning and degreasing machine tools and parts.
- Odorless Mineral Spirits are petroleum-derived mineral spirits that have been further refined to remove toxic aromatic compounds including benzene and toluene.
- OMS has an initial boiling point of about 340F (171-178° C.) and a specific mass of about 0.76 g/cc, and is often recommended for applications where humans have close contact with the solvent, including oil painting, ink printing and addition to barbecue charcoal as an easily ignited lighter fluid.
- OMS has been used for many years to initiate combustion of more difficult to ignite regular fuels including charcoal, coal, and pellet fuels, for example.
- OMS charcoal lighter has dominated the marketplace and has been sold for many years by a number of companies including the Kingsford Products Company (Oakland, Calif.), Royal Oak Enterprises, LLC (Roswell, Ga.), Reckitt and Coleman (Wayne, N.J.) and Duraflame Inc. (Stockton, Calif.).
- User directions suggest that an amount of OMS fluid equal to approximately 10% the weight of the charcoal should be applied to the charcoal (1.6 fluid oz per pound of charcoal). Therefore, a quart of the fluid is sufficient to light approximately one 20 lb. bag of charcoal.
- Biodiesel fuel can be used in standard diesel engines, and is thus distinct from vegetable and waste oils used to fuel converted diesel engines. Biodiesel can be used alone (termed “B100 fuel”), or blended with petroleum hydrocarbon fuels (e.g., B20 containing 20% biodiesel+80% petroleum diesel fuel). Blends of less than 20% biodiesel can be used in diesel equipment with no, or only minor, modification. Biodiesel can also be used as an alternative to petroleum-based heating oil.
- B100 fuel petroleum hydrocarbon fuels
- B20 containing 20% biodiesel+80% petroleum diesel fuel blended with petroleum hydrocarbon fuels
- Blends of less than 20% biodiesel can be used in diesel equipment with no, or only minor, modification. Biodiesel can also be used as an alternative to petroleum-based heating oil.
- Fatty acid esters contain alkyl chains of varying length, e.g., C 4 -C 18 that may be esterified to methyl, ethyl or propyl moieties.
- Fatty acid methyl esters have been assigned standard CAS registration numbers based upon the number/range of carbon atoms in their fatty acids as follows: C 6 -C 12 , CAS Reg. No. 67762-39-4; C 10 , CAS Reg. No. 110-42-9; C 12 , CAS Reg. No. 111-82-0; C 12 -C 18 , CAS Reg. No. 68937-84-8; and C 16 -C 18 , CAS Reg. No. 85586-21-6.
- Fatty acid methyl esters are aliphatic organic esters primarily prepared by the reaction of carboxylic fatty acids derived from natural fats and oils and methanol in the presence of a base catalyst. The resulting esters can be subsequently processed into various alkyl range cuts by fractional distillation. Fatty acid methyl esters are used extensively as intermediates in the manufacture of detergents, emulsifiers, wetting agents, stabilizers, textile treatments, and waxes, among other applications. Lesser volumes of fatty acid methyl esters are used in a variety of direct and indirect food additive applications, including the dehydration of grapes to produce raisins, synthetic flavoring agents, and in metal lubricants for metallic articles intended for food contact use. Fatty acid methyl esters are also used as intermediates in the manufacture of a variety of food ingredients.
- thermo-precipitated monoglycerides as rheology modifiers that thicken hydrophobic liquid fuels.
- a hydrophobic liquid such as a petroleum-based fuel
- these monoglycerides are capable of forming micron-sized solid microparticles that can thicken the liquid.
- the compositions and methods therein describe, in certain embodiments, the use of molten monoglycerides that are added and dispersed at an elevated temperature, e.g., 70-80° C., into a flammable fuel.
- certain embodiments are directed to reducing the hazard associated with dispersing an ingredient in a flammable hydrophobic liquid, e.g., so that neither the ingredient nor the liquid are at a temperature above the flash point of the liquid.
- Applicant has devised various compositions herein, including compositions that allow dispersal of solid monoglycerides at ambient temperature in a flammable fuel in which the chemistry and the physical structure of the monoglycerides have been altered to allow such dispersal and thickening of a fuel at ambient temperature.
- Monoglycerides whose molecules have been commingled and/or chemically complexed with glycerine are used in certain embodiments of the invention for thickening hydrophobic liquids such as liquid fuels.
- MG Monoglycerides
- two glycerine molecules can be complexed with an MG molecule by an associative hydrogen-bonding mechanism.
- This hydrogen bonding of glycerine (abbreviated “G”) to MG is especially effective in disrupting the continuous waxy structure of unmodified MG solids that prevents the solids from being dispersed directly into many hydrophobic liquids such as mineral spirits to thicken these liquids.
- MG molecules also known as monoacylglycerols
- monoacylglycerols are formed from one fatty acid molecule covalently bonded to a three carbon glycerol backbone via an ester linkage. Depending on whether the ester-linked fatty acid occupies the middle or the end position on the glycerol backbone, the MG is either a 2-monoacylglycerol or a 1-monoacylglycerol.
- Monoacylglycerols may be produced by either chemical synthesis or by an enzymatic process. Enzymatic treatment of triglyceride (fat) and diglyceride molecules by pancreatic lipase for example, yields 2-monoglycerides.
- Synthetic interesterification that combines triglycerides with an excess of free glycerine in the presence of NaOH typically yields a largely random distribution of fatty acid ester locations on the glycerol backbone.
- the reaction also may yield a mixture of MGs combined with reactants, catalysts and undesirable by-products in some cases that must be removed before the MGs can be used in commercial applications. It is common for MGs to be fractionated and purified by vacuum distillation. MGs can be synthetically produced from either animal or vegetable-derived fats.
- saturated fats or fully hydrogenated fats are commonly interesterified with glycerine, and the resulting MGs also may be predominantly saturated.
- saturated fatty acid MGs may be abbreviated “SFA-MGs.” They contain predominantly 12, 14, 16 and 18 carbon ester-linked fatty acids and have melting points ranging between approximately 50° C. and 68° C.
- SFA-MGs saturated fatty acid MGs
- MGs can be produced by interesterifying fully hydrogenated palm oil with glycerine, and subsequently purifying and distilling the MGs to eliminate both non-reacted reactants and by-products (including fat, glycerine, sodium hydroxide, diglycerides and other by-products).
- MGs and in particular those containing saturated fatty acids with twelve to eighteen carbon atoms, are waxy solids typically added to edible oils in small quantities by heating the glycerides alone or combined with an edible oil to a temperature above the melting point, e.g., 60° C. or above, prior to mixing with other ingredients.
- MG and diglyceride molecules are generally amphiphilic in character, containing both hydrophobic and hydrophilic portions. They typically serve as emulsifiers to help stabilize a variety of mixtures of dissimilar ingredients that are often liquid or semi-liquid. For example, a combination of MG, edible fats and oils, water and flavorings that would otherwise not mix, can be combined to form buttery table spreads.
- MGs are found in a wide variety of food products including bakery products, beverages, ice cream, shortenings, margarines, confections, and whipped toppings, for example.
- a margarine emulsion a melted MG may be blended with oil and water to produce stable micelles that contain microdroplets of water and other ingredients that are surrounded by a continuous oil phase.
- the stabilizing emulsifier molecules tend to concentrate at the interface between the suspended water droplets and the surrounding oil.
- MG compositions and methods have been discovered whereby a solid material can be produced composed of micron-sized MG microparticles in which glycerine molecules have been hydrogen-bonded to MG molecules in a substantially water-free mixture to form a new chemical complex.
- the glycerine molecules and/or the MG molecules may be purified. These microparticulate solids may be stable and can be produced ahead of time for later use.
- the complex may be produced by heating and melting together certain proportions of purified glycerine and MG in the substantial absence of water, and subsequently cooling the melt to room temperature.
- the resulting solid material composed of microparticles may be stored at room temperature for an extended time, and some time thereafter may be dispersed at room temperature in a fuel or other hydrophobic liquid.
- MG compositions and methods described herein incorporating glycerine may offer advantages over methods that require dispersal of molten MG at elevated temperature into a flammable fuel using high shear dispersal equipment.
- a purified MG may be combined in suitable proportions with glycerine, and hydrogen bonded at the molecular level, converting the physical structure of the MG from an amorphous waxy solid to a microparticulate solid that is readily dispersible in a hydrophobic liquid.
- Various aspects of the present invention provide, inter alia, advantageously supplemented hydrophobic fuels that are thickened by addition of a novel agent comprising or consisting essentially of glycerine-modified SFA-MGs.
- the SFA-MG ingredient typically contains C 12:0 , C 14:0 , C 16:0 , and/or C 18:0 fatty acids.
- the SFA-MG may be purified.
- the SFA-MGs may be heated, melted, and combined with a suitable and sufficient proportion of glycerine (e.g., 2 parts by weight mixed C 16:0 and C 18:0 MGs to 1 part by weight glycerine), e.g., in a substantially water-free mixture.
- the melted and/or commingled mixture of glycerine and monoglyceride may be cooled to form a solid that, surprisingly, has a microparticulate structure that facilitates dispersal, rather than the characteristic amorphous waxy structure of MGs.
- the glycerine-modified MG microparticulate solids are remarkably stable in some embodiments; for example, the MG microparticulate solids may be readily dispersible at room temperature in OMS petroleum lighter fluid and other hydrophobic liquids, whereas the same MG lacking glycerine is not dispersible at room temperature.
- the microparticulate-thickened OMS fuel compositions are, for example, useful for lighting charcoal fires, such as in charcoal grills.
- One aspect of the invention provides a fuel composition that includes at least one hydrophobic liquid and an effective amount of at least one SFA-MG agent combined with a suitable amount of glycerine.
- the combined glycerine-MG agent dispersed in the hydrophobic liquid may cause effective thickening of the fuel composition, using, for example, as little as 2%-4% by weight MG combined with 1%-2% glycerine.
- the MG material may be heated, melted and combined with glycerine, e.g., in a substantially water-free mixture (which may in some cases facilitate hydrogen-bonding between the MG and the glycerine), before being cooled to form a solid, e.g., as a microparticulate agent;
- the liquid being supplemented with the microparticulate agent may be a hydrocarbon- or fatty acid ester-based hydrophobic liquid, and/or the hydrophobic liquid may be combustible;
- the MG agent may contain predominantly SFA-MGs;
- the MG agent may contain predominantly SFA-MGs and may not contain a significant level of fatty acid di- or tri-glycerides;
- the MG agent may contain a combination of SFA-MGs and disaturated fatty acid diglycerides;
- the MG agent may contain a combination of SFA-MGs and disaturated fatty acid triglycerides; and/or the MG agent may contain a
- the composition includes glycerine (G) molecules commingled and/or hydrogen-bonded with MG molecules in ratios by weight of G:MG of between 1:1 to 1:1.5, 1:1.5 to 1:2.0, 1:2.0 to 1:2.5, 1:2.5 to 1:3.0, 1:3.0 to 1:3.5, and 1:3.5 to 1:4.0, and/or any combinations thereof (e.g., 1:1 to 1:4).
- G glycerine
- the MG ingredient typically contains either C 10:0 , or C 12:0 , or C 14:0 , or C 16:0 , or C 18:0 fatty acids or any combination thereof.
- the hydrophobic liquid composition containing the composite G+MG agent may include 1-15%, 2-15%, 3-15%, 5-15%, 1-12%, 2-12%, 3-12%, 4-12%, 5-12%, 7-12%, 1-10%, 2-10%, 3-10%, 4-10%, 2-8%, 2-6%, 3-8%, 3-6%, 3-5%, 4-8%, or 4-6% by weight of the agent;
- the combustible hydrophobic liquid may be or include an aliphatic hydrocarbon liquid, for example, an alkane hydrocarbon liquid, odorless mineral spirits, or paraffin oils;
- the hydrophobic liquid may be or include an fatty acid alkyl ester hydrophobic liquid, for example, a fatty acid mono-alkyl ester liquid such as a liquid in which some, most, or substantially all of the fatty acid esters (e.g., at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% of the fatty acid mole
- At least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% by weight of the MG agent may be glycerol monostearate or glyceryl monopalmitate or a mixture of glyceryl monostearate and glyceryl monopalmitate.
- other MG agents may be present in addition and/or instead of glycerol monostearate or glyceryl monopalmitate.
- the glycerine-containing composite MG agent also may contain at least one saturated fatty acid-containing diglyceride, e.g., glyceryl distearate, glyceryl dipalmitate, glyceryl palmitostearate and/or combinations thereof; the agent also may contain a fat that is solid at room temperature, for instance, containing trisaturated triglycerides, e.g., tristearin, tripalmitin, palmitodistearin, stearodipalmitin, and/or combinations thereof; and/or the agent also may contain at least one saturated fatty acid-containing diglyceride (e.g., as just listed above) and/or at least one trisaturated triglyceride (e.g., as just listed above).
- the agent also may contain at least one saturated fatty acid-containing diglyceride (e.g., as just listed above) and/or at least one trisaturated triglyceride (e.g., as just
- the glycerine-containing composite MG agent may be supplemented with a limited amount (between 5% and 50% by weight) of at least one hydrophobic liquid that is soluble in the remainder of hydrophobic liquid being thickened.
- This supplementation with a hydrophobic liquid typically acts to accelerate the disintegration and dispersal of the solid composite MG agent in the bulk of the hydrophobic liquid being thickened.
- a limited amount of light mineral oil e.g., 25% by weight, that is miscible in a chemically similar (but lower molecular weight) OMS fuel being thickened, can be combined with 75% by weight of the glycerine-containing composite MG thickening agent to accelerate dispersal of the thickener in the OMS fuel.
- Another aspect of the invention provides a method of thickening a hydrophobic fuel, a combustible fuel, and/or a liquid fuel.
- the method involves, in some cases, combining a solution containing a hydrophobic liquid with an effective amount of at least one solid glycerine-modified MG microparticulate agent and shear-dispersing the agent until the microparticulate agent (including molecules of glycerine-modified MG released from the microparticulate agent) is homogeneously dispersed therein, thereby forming a thickened or gelled fuel.
- the hydrophobic liquid may be a hydrophobic liquid fuel.
- the glycerine-MG composite agent may be dispersed in the hydrophobic liquid at ambient temperature; the glycerine-MG composite agent may be dispersed in the hydrophobic liquid under conditions of temperature, moderate or high shear mixing, and the physical form of the solid composite agent that the agent is fully dispersed as microparticles in the liquid within 5 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, or 60 seconds, or with 2 minutes, 3 minutes, or 5 minutes of combining the agent and the liquid; the glycerine-MG composite agent may be added to the hydrophobic liquid in the form of a solid; the MG agent may be added to the hydrophobic liquid as a broken solid (the use of small particles, e.g., flakes, small irregular chunks, or solidified droplets may be beneficial to reduce dissolution time, in some embodiments); immediately before rapid mixing of the hydrophobic liquid with the glycerine-MG composite agent, the temperature may be at least 1° C., 2° C., 3° C.
- the temperature may be at least 10° C., 15° C., 20° C., 25° C., 35° C., or 40° C. or is in a range of 10-20° C., 15-25° C., 20-30° C., 25-35° C.
- the glycerine-MG composite agent may be added to the hydrophobic liquid at a temperature at least 10° C., 7° C., 5° C., 4° C., 3° C., 2° C., or 1° C. below the solvent-free melting temperature of the glycerine-MG composite agent.
- the hydrophobic liquid may be a hydrophobic liquid fuel in certain cases.
- a hydrophobic liquid may be mixed with glycerine molecules and MG, e.g., to form a ternary mixture or a solid.
- the hydrophobic liquid may be a non-aqueous, and/or a fuel, e.g., a hydrophobic fuel, a combustible fuel, and/or a liquid fuel.
- the hydrophobic liquid in the mixture or solid may be substantially similar or even identical to one which the mixture or solid is targeted, e.g., for thickening purposes.
- the hydrophobic liquid may be useful to facilitate dispersion in the target liquid, e.g., due to chemical similarity (or chemical identity).
- the hydrophobic liquid may be present in any suitable quantity in the mixture or solid.
- the hydrophobic liquid may be present at less than about 50%, less than about 40%, less than about 30%, less than about 20%, or less than about 10% by weight. In one embodiment, the hydrophobic liquid is present between about 10% and about 50%.
- the method includes rapidly mixing a first quantity of the glycerine-MG composite agent dispersed in a first hydrophobic liquid, with a second volume of a second hydrophobic liquid, thereby forming a mixed hydrophobic liquid.
- the first and second liquids may be the same or different.
- the temperature of the mixed hydrophobic liquid may be below the solvent-free melting temperature of the glycerine-MG composite agent, the first volume may be less than the second volume, e.g., no more than 0.01, 0.02, 0.05, 0.07, 0.10, 0.15, 0.20, 0.25, 0.30, or 0.40 times the second volume.
- the first hydrophobic liquid may be a hydrophobic liquid fuel
- the second hydrophobic liquid may be a hydrophobic liquid fuel.
- the dispersed microparticulate agent may be or include glyceryl monostearate, glyceryl monopalmitate, or both combined with glycerine (e.g., melted together, mixed and cooled); the dispersed microparticulate agent may contain MG (e.g., as just listed) and also may in some cases contain at least one saturated fatty acid-containing diglyceride (e.g., glyceryl distearate, glyceryl dipalmitate, glyceryl palmitostearate and combinations thereof) and/or the agent also may contain a fat that is solid at room temperature containing trisaturated triglycerides (e.g., tristearin, tripalmitin, palmitodistearin, stearodipalmitin, and combinations thereof); the fuel may be a hydrocarbon-based liquid fuel, an alkyl ester-based liquid fuel or a combination thereof; the alkyl ester-based liquid fuel may be a fatty acid-containing dig
- Another aspect provides a method of lighting barbecue charcoal (e.g., shaped charcoal briquettes or irregular lump charcoal).
- the method involves applying an effective amount of a thickened or unthickened fuel composition to a first layer of the barbecue charcoal, adding a second layer of the barbecue charcoal on top of the first layer, and igniting the fuel composition on the first layer.
- the quantity of charcoal in the first and second layers together may be at least 1 pound, 2 pounds, 3 pounds, 4 pounds, or 5 pounds of charcoal or 1-3 pounds or 2-4 pounds; and/or the effective amount of fuel composition may be 1 to 10 fluid ounces, 1 to 8 fluid ounces, 1 to 6 fluid ounces, 1 to 5 fluid ounces, 2 to 10 fluid ounces, 2 to 8 fluid ounces, 2 to 6 fluid ounces, 3 to 10 fluid ounces, 3 to 8 fluid ounces, or 4 to 10 fluid ounces.
- the charcoal may rest on a non-combustible support such as a grate or support platform (which may be perforated or otherwise include air passage through the support, for example, in a barbecue grill, hibachi, or similar device); the weight amount of the fuel composition which is applied may be approximately 0.05 to 0.15, 0.05 to 0.10, or 0.10 to 0.15 times the weight of the charcoal in certain embodiments.
- a non-combustible support such as a grate or support platform (which may be perforated or otherwise include air passage through the support, for example, in a barbecue grill, hibachi, or similar device)
- the weight amount of the fuel composition which is applied may be approximately 0.05 to 0.15, 0.05 to 0.10, or 0.10 to 0.15 times the weight of the charcoal in certain embodiments.
- a fuel composition that contains at least one hydrophobic liquid fuel and an effective amount of at least one saturated fatty acid MG agent (abbreviated “SFA-MG”), in which the heat-solubilized MG agent is rapidly and substantially diluted into a much cooler liquid fuel, causing precipitation of the MG as microparticles in the liquid fuel, and thereby causing thickening.
- SFA-MG saturated fatty acid MG agent
- the hydrophobic liquid fuel may be a hydrocarbon fuel such as aliphatic odorless mineral spirits or paraffin oil, or the fuel is a fatty acid alkyl ester-based fuel such as a C 18 , C 16 or a C 10 and C 8 fatty acid methyl ester-based fuel.
- the fuel may contain between 2% and 6% by weight of at least one SFA-MG agent such as glyceryl monostearate and/or glyceryl monopalmitate.
- the fuel may also contain between 1% and 10% by weight of at least one saturated fatty acid-containing diglyceride in some cases.
- a dissolved (e.g., heat-solubilized) MG agent to be precipitated (e.g., rapidly precipitated) as microparticles in a larger volume of cool hydrophobic liquid fuel to cause its thickening.
- MG material may be purified.
- the MG material may be melted, mixed, and/or molecularly commingled with glycerine, which may allow hydrogen bond formation between the glycerine hydroxyl groups and the two hydroxyl moieties present in the MG molecule.
- glycerine, G, and MG are combined, in accordance with certain embodiments of the invention, in a mixture such that the weight ratio of G to MG is between approximately 1:1 and 1:4, such as approximately 1:2.
- G and MG may be combined in a mixture such that the molar ratio of G to MG is between approximately 1:1 and approximately 4:1.
- the mixture may be heated to a temperature above the melting point of the MG, mixed to allow the molecules to commingle, and subsequently allowed to cool.
- the mixture may spontaneously solidify as a mass of micron sized solid microparticles containing an associative chemical complex of hydrogen-bonded G and MG.
- MG material of glyceryl monostearate and glyceryl monopalmitate (solidified as microparticles) are able to sequester up to 1.0 part by weight glycerine.
- This weight ratio corresponds to a molar or molecular ratio of about two molecules of G per one molecule of MG.
- a microscopic examination of the cooled, solidified mixture shows microdroplets of free glycerine scattered throughout the field of MG microparticles.
- the full capacity of MG microparticles to bind (i.e., hydrogen-bond) G is believed to correspond to each MG molecule with its two free hydroxyl groups hydrogen-bonding two molecules of G. It is believed that this G-MG hydrogen-bonding may also be instrumental in disrupting the normal solidification of MG as a continuous waxy solid. Rather, the G-MG complex may solidify as a mass of micron-sized microparticles that are readily dispersed at ambient and even cool temperatures (well below flash point temperatures for safety) in hydrophobic liquids such as mineral spirits-based fuels and fatty acid methyl ester fuels with shear-agitation, in accordance with certain embodiments of the invention.
- Molar ratios may be useful in some cases in demonstrating chemical stoichiometry and complex formation.
- the molar ratio of G/MG provides the number of glycerine (G) molecules that can hydrogen-bond with a monoglyceride (MG) molecule.
- Weight ratios may be used in some cases to provide directly measurable quantities of material for formulation purposes.
- the MG average molecular weight is about 350 daltons, while the molecular weight of G is only 92 daltons.
- a 1:1 molar ratio of G to MG would equal a G/MG weight ratio of 92/350 or 1/3.8.
- certain embodiments of the present invention provide a simplified and safer process for thickening a flammable hydrophobic fuel employing MGs.
- the fuel is neither heated, nor is the fuel combined with a hot ingredient.
- the new process is based on Applicant's initial discovery that 2 parts by weight of a typical SFA-MG produced from fully hydrogenated palm oil containing 16 and 18 carbon fatty acids (palmitate and stearate MGs) could be converted into “microparticulate solids” by melting and mixing these MGs with a suitable proportion, i.e., approximately 1 part by weight of glycerine.
- this hydrogen-bonded glycerine-modified MG material (2:1 weight ratio or 1:2 molar ratio of MG:G) can be conveniently introduced at room temperature into an OMS fuel in some embodiments, for example, using shear-dispersal.
- Amorphous microparticles some of which are less than one micron in diameter, may contain the glycerine-MG complex, and may be visible in some embodiments by phase contrast microscopy of the fuel. For example, on a microscope slide, 3%-4% by weight of these microparticles suspended in OMS fuel can be seen to move in a thixotropic (shear-thinning) manner, forming a visible and substantially static network of particles that acts to thicken the fuel as liquid movement slows.
- compositions and methods are described herein for producing and using microparticulate MGs as a thickening agent for hydrophobic liquids such as OMS.
- a useful thickening ingredient is produced when a suitable amount of glycerine (abbreviated “G” herein) is mixed and its molecules commingled with a certain amount of heated and melted MG.
- G glycerine
- one part by weight glycerine combined with 2 parts by weight MG corresponds to a ratio of approximately 2 molecules glycerine per molecule of MG.
- the commingling of G and MG in this 1:2 ratio is believed to produce a hydrogen-bonded chemical complex in which little or no free glycerine can be seen microscopically using cross-polarized light, as two molecules of G appear to bond with each molecule of MG to produce uniformly sized microparticles of G 2 MG. Further addition of G may result in visible glycerine microdroplets that do not bind or become integrated into MG microparticles.
- the choice of MG is usually selected to have a melting point that is substantially elevated above room temperature (e.g., above 50° C. or 60° C.), and as such is usually a saturated fatty acid MG such as glyceryl monostearate and/or monopalmitate.
- the re-solidified G+MG mixture When mixed, melted and subsequently cooled and solidified, the re-solidified G+MG mixture has the unusual property of solidifying as a microparticulate mass of material.
- This material which may be formed, or consist essentially of hydrogen-bonded glycerine (G) and MG molecules in some cases, can be added and dispersed at ambient temperature into a flammable liquid fuel to produce a fuel that is thickened with G-MG-containing microparticles, in accordance with certain embodiments of the present invention.
- G hydrogen-bonded glycerine
- MG hydrogen-bonded glycerine
- the material may disperse as single microparticles and small groups of microparticles.
- the weight proportions of G and MG that are combined to form a microparticulate G-MG complex may be varied depending upon the choice of MG. For example, a weight ratio of approximately one part G to 2 parts MG is generally useful for MG derived from a fully hydrogenated palm oil that yields predominantly glyceryl monostearate and glyceryl monopalmitate. If excess glycerine is blended into the melt (e.g., 1 part G+1 part MG), the resulting product examined using polarized light microscopy shows excess free glycerine microdroplets distributed among a continuous visual field of G-MG microparticles.
- the weight ratio of G to MG may be about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, or about 1:5. In some cases, the weight ratio of G to MG may be between about 1:1 and about 1:5, between about 1:1 and about 1:4, or between about 1:1 and about 1:3.
- glycerine functions neither as a solvent nor as an emulsifier for the MG, but rather as a hydrogen-bonding complex-forming agent that may act as a disruptive “spacer molecule” between neighboring MG molecules. Regardless of the actual mechanism, the presence of glycerine may alter the association among groups of MG molecules.
- the present invention is generally directed to a mixture of glycine and at least one MG having a molar ratio of between approximately 1:1 and approximately 10:1, between approximately 1:1 and approximately 7:1, between approximately 1:1 and approximately 6:1, between approximately 1:1 and approximately 5:1, between approximately 1:1 and approximately 4:1, or between approximately 2:1 and approximately 4:1.
- the molar ratio may be about 1:5, about 1:4, about 1:3, about 1:2, about 1:1, about 2:1, about 3:1, about 4:1, or about 5:1.
- glycerine a three carbon and three hydroxyl group-containing polar substance
- MG may beneficially be combined (e.g., at the molecular level) with MG to form a binary or ternary complex for example, by heating, melting, mixing and finally cooling in a substantially water-free blend, approximately:
- the very small average diameter of the microparticles formed with MGs and glycerine may allow these microparticles to remain dispersed in some cases in hydrophobic liquids, e.g., almost indefinitely without settling.
- the use of a MG and glycerine in forming a complex may provide a significant advantage over the use of MG alone.
- a useful MG+glycerine complex may be formulated by heating and melting together approximately 2 parts by weight of a MG such as Myverol 18-04 (manufactured by Kerry Ingredients and Flavours, Beloit, Wis.) with 1 part by weight glycerine.
- the MG emulsifier e.g., Myverol 18-04 may contain glyceryl monostearate and/or glyceryl monopalmitate. Formulations containing higher or lower proportions of glycerine and emulsifier may also be constituted in some embodiments of the invention.
- Glycerine (aka, glycerol, or glycerin, C 3 H 8 O 3 ) is a relatively low molecular weight (MW of 92) water-soluble, polar liquid with low vapor pressure. It is a colorless, odorless, edible, sweet-tasting hygroscopic liquid that is widely used in pharmaceutical preparations. Its three hydroxyl groups are responsible for its water-miscibility and hygroscopic nature. Glycerine is a precursor for synthesis of triglycerides and of phospholipids in the liver and adipose tissue.
- MG has an average molecular weight of ⁇ 350.
- This stoichiometry suggests that a hydrogen-bonding association may occur between two glycerine molecules and the two free —OH moieties present in each MG molecule. Without wishing to be bound by any theory, it is believed that the hydrogen-bonding association differs from chemical solubility in which a solute and solvent are not constrained by the formation of such a complex.
- the MGs that solidified following cooling of the above-described melted mixtures of MGs prepared with glycerine were compared by phase contrast light microscopy and polarizing light microscopy.
- the glycerine-associated MGs solidified as masses of countless microscopic spherules (also known as “microspheres”) each measuring less than 5 microns, many measuring approximately 2-4 microns, and many others measuring approximately 1-2 microns or less in diameter.
- the microspheres appeared amorphous under non-polarized light, phase contrast illumination.
- compositions and methods described herein allow the thickening and/or gelling of fuel compositions comprising hydrophobic liquids, such as hydrophobic liquid fuels. This may be achieved in some embodiments using cost-effective and/or environmentally sustainable agents for this purpose.
- thickened fuel compositions may be used to initiate the combustion of solid fuels that are more difficult to ignite, including but not limited to charcoal and irregular lump charcoal.
- the fuel composition may include a hydrophobic liquid in some cases.
- the hydrophobic liquids may comprise fuels, which include, but are not limited to, hydrocarbon fuels such as alkane-based odorless mineral spirits, paraffin oil or mineral oil, and ester-type biofuels such as mono-alkyl esters of long chain fatty acids of animal or vegetable origin (also known as biodiesel fuels).
- hydrocarbon fuels such as alkane-based odorless mineral spirits, paraffin oil or mineral oil
- ester-type biofuels such as mono-alkyl esters of long chain fatty acids of animal or vegetable origin (also known as biodiesel fuels).
- OMS Odorless Mineral Spirits
- OMS can be improved by thickening the OMS fluid to achieve one or more of the following:
- Typical current directions for use of an OMS lighter fluid call for a generous amount of the fluid to be applied to the charcoal (e.g., 1.6 oz fluid per 16 oz charcoal).
- Traditional lighter fluid is nearly instantly absorbed, and unless a large amount of the fluid is applied, either the charcoal is difficult to ignite or the fire burns too briefly to ignite the charcoal.
- OMS By substantially saturating the charcoal with OMS, the fire is more easily ignited and the fuel burns long enough to ignite the charcoal.
- the use of so much OMS (10% by weight of the charcoal) may be considered wasteful, and the charcoal typically continues to emit mineral spirits fuel odors even after grilling of food has commenced.
- much of the heat generated from combustion of the fluid rises away from the charcoal rather than rising into the charcoal to initiate its combustion.
- the present invention facilitates, in one set of embodiments, various techniques for overcoming these difficulties.
- OMS lighter fluid (as well as other suitable hydrophobic liquids, such as hydrophobic liquid fuels, for example, mineral oil) can beneficially be thickened, in accordance with one set of embodiments, by dispersing a remarkably small proportion (e.g., 2%, 3%, or 4% by weight) of an agent comprising one or more SFA-MGs that have been pre-combined by melting and/or commingling SFA-MGs, i.e., molecules thereof, with a suitable amount of glycerine molecules.
- SFA-MG and glycerine molecules to form hydrogen bonds in which up to two glycerine molecules can bond with each MG molecule.
- the resulting G 2 MG molecular complex forms stable microparticulate solids upon cooling and solidifying.
- the microparticulate solids are partially or fully dispersible in an OMS lighter fluid (and/or other suitable hydrophobic liquid), and when added at a sufficient level (e.g., 1%-10% by weight) and shear-blended in the liquid, useful thickening of the liquid occurs.
- OMS fluid or other hydrophobic liquid
- thickening may increase over a matter of hours or over the course of a day or two before reaching maximum thickening.
- the hydrophobic liquid may be a fuel.
- the hydrophobic liquid may also be a hydrocarbon-containing liquid in certain embodiments, for example, OMS, or paraffin oil or mineral oil, available commercially in both light and heavy grades.
- the fuel is combustible, i.e., the fuel is susceptible to combustion or reaction with oxygen in the air, and often will burn in an open flame when ignited and exposed to the air (i.e., the fuel may be flammable in some cases).
- a flame from a match under ambient conditions, e.g., at room temperature (25° C.) and normal atmospheric pressure (1 atm)
- a fuel may be ignited upon contact with a flame from a match (or other ignition source) under ambient conditions, e.g., at room temperature (25° C.) and normal atmospheric pressure (1 atm), a fuel may be ignited.
- a fuel may have a flash point or a fire point of less than about 90° C., less than about 80° C., less than about 70° C., less than about 60° C., less than about 50° C., or less than about 40° C.
- the flash point is the lowest temperature at which the material will ignite or combust when exposed to an external ignition source
- the fire point is the lowest temperature at which the material will, after being initially ignited by an external ignition source, continue to burn or combust for at least 5 seconds after exposure and removal of the external ignition source.
- the fuel is liquid and flows to conform to the outline of its container, although the fuel may be relatively viscous in some cases (i.e., having a viscosity that is greater than the viscosity of water).
- the fuel may also be viscoelastic and/or solid in some embodiments. Most, but not all, fuels are inedible, i.e., such fuels are not routinely eaten by people, and consumption of such fuels would result in adverse biological effects, including toxicity, poisoning, liver damage, organ failure, or death.
- the solid agent comprising MG and glycerine may be dispersed in the hydrophobic liquid in a number of different ways.
- the agent may be added in solid form to the hydrophobic liquid at ambient temperature, which liquid may be agitated or shear-blended sufficiently for dispersal of the agent as microparticles comprising MG that has been hydrogen bonded with glycerine.
- the agent comprising MG and glycerine is melted, added and dispersed in the hydrophobic liquid at a temperature below the precipitation temperature of the MG-glycerine complex to cause rapid precipitation of microparticulate solids or larger solid particles that subsequently disaggregate into microparticles.
- the MG-glycerine agent is melted and added to warmed hydrophobic liquid that is at a temperature above the precipitation temperature of the agent in the hydrophobic liquid.
- the result is that the agent is dissolved in hydrophobic liquid above the precipitation temperature.
- the agent may be precipitated in some embodiments by cooling, usually rapid cooling, for example by mixing the warmed liquid/agent mixture into a quantity of cooler hydrophobic liquid. This may be performed such that the combination has sufficient quantity and sufficiently cool temperatures so that the combination of the two results in a mixed liquid below the precipitation temperature of the agent.
- OMS is a low viscosity petroleum liquid that tends to dribble from the aperture of a container and contaminate the outside of the container and one's hands.
- compositions disclosed herein at least in certain cases, has no tendency to dribble, e.g., due to their thickened state.
- most of the monoglyceride-gelled or semi-gelled fluid may be retained as a visible coating, e.g., on the surface of the charcoal (or other solid fuel).
- This visual cue may be particularly obvious in embodiments where the thickener makes the fluid white and opaque, and this visual cue may be used to give a user an immediate indication of where and how much of the composition has been applied.
- the applied fuel composition that is applied to the surface of charcoal briquettes may be more easily ignited for an extended time interval (e.g., in contrast to traditional OMS fluids that have a tendency to disappear from the surface as it is absorbed therein).
- one set of embodiments is generally directed to gelled compositions that melt at approximately 133° F.
- the composition may include monoglyceride-thickened mineral spirits.
- the composition comprising the MG gel may melt, and the liquefied fuel may ignite while being absorbed into the surface of the charcoal, e.g., where it can burn and/or ignite nearby charcoal.
- the former problem of rapid and/or deep absorption of a traditional liquid lighter fluid such as OMS fluid into charcoal can be avoided using certain embodiments of the invention, and/or a smaller quantity of the thickened fuel composition can be applied to the charcoal (and/or another suitable solid fuel), to allow for ignition of the surface.
- the fuel compositions consist essentially of carbon, hydrogen and oxygen atoms that, upon complete combustion, produce water and carbon dioxide.
- the fuel compositions in some cases, are free of heavy metals and/or are free of chlorinated and other halogenated compounds that, upon burning, could produce dioxin and other toxic substances.
- the fuel compositions are expected to meet California and/or Federal Volatile Organic Compounds (VOC) emission standards for charcoal lighter material products in certain embodiments of the invention. Accordingly, the fuel compositions are able to, in some embodiments, produce no more than 0.020 pounds VOC per start according to the California South Coast Air Quality District Rule 1174 Ignition Method Compliance Certification Protocol, dated Feb. 27, 1991, or an equivalent amount under a subsequent Ignition Method Compliance Certification Protocol or alternate protocol. In some cases, the fuel compositions produce no more than 0.01 pounds, or no more than 0.005 pounds VOC per start under the cited protocol.
- the amount of fuel composition required for lighting a fire may vary, e.g., between approximately 1 and 10 fluid ounces.
- the amount of fuel composition applied to a solid fuel such as charcoal or fireplace wood will vary between 2 fluid ounces and 6 fluid ounces, or between 3 fluid ounces and 5 fluid ounces.
- the quantity of fuel composition can vary between 2-16 fluid ounces, 4-10 fluid ounces, 4-12 fluid ounces, 6-12 fluid ounces, or 6-10 fluid ounces.
- the quantity of fuel composition is selected to provide at least 10 minutes, 15 minutes, or 20 minutes of burn time.
- hydrophobic liquids such as hydrophobic liquid fuels can be thickened to produce a fuel composition using a remarkably low level, e.g., 2%-4% by weight, of an agent such as described herein, using a simple mechanical blending process for introducing the agent into the liquid, for example, a liquid fuel.
- agents that are predominantly SFA-MGs have been found quite effective.
- Agents containing primarily C 16 and/or C 18 fatty acid MGs can be advantageously used in some cases.
- C 16 and C 18 saturated fatty acid-containing distilled MGs e.g., glyceryl monopalmitate and/or glyceryl monostearate
- mixed mono- and diglycerides e.g., prepared from hydrogenated palm oil.
- diglycerides as well as MGs, C 18:0 and/or C 16:0 saturated fatty acids may be used in some embodiments. Some of these are commercially available.
- the glycerides prepared from fats whose fatty acid carbon chains are longer may have higher melting points than glycerides prepared from fats whose fatty acid carbon chains are shorter (e.g., C 12:0 and C 14:0 ) and/or unsaturated (e.g., oleic acid, C 18:1 ).
- Some commercially-available preparations comprising diglycerides may contain glyceryl dipalmitate, glyceryl distearate and/or glyceryl palmitostearate.
- a MG that contains low levels of diglycerides can be used in some embodiments as an effective thickening and gelling agent, often at a final concentration of approximately 3-5% by weight commingled with glycerine at final concentrations of approximately one-half of the glyceride concentrations, e.g., 1.5-2.5%. In other embodiments, however, other materials may also be present.
- a fully hydrogenated palm oil-derived MG e.g., MyverolTM 18-04 from Kerry Ingredients and Flavors, Inc., Beloit, Wis.
- MGs e.g., MyverolTM 18-04 from Kerry Ingredients and Flavors, Inc., Beloit, Wis.
- MGs essentially glyceryl monopalmitate and glyceryl monostearate, and having a melting point of 66° C.
- an immobilized array of very small amorphous particles having a diameter of less than 5 microns in diameter are observed. Most of the particles are 2-4 microns in diameter, 1-2 microns in diameter, and smaller. Dispersed in OMS fuel and viewed under the microscope, the particles appear to loosely bind to one another and are surprisingly effective in sequestering and thickening the fuel.
- the fuel compositions described herein can be produced in a number of different methods, including industrial scale methods, in various embodiments of the invention.
- a continuous-flow process suitable for commercial scale production of thickened lighter fluid may be used under some conditions.
- the complexed MG-glycerine thickening agent solids and a hydrophobic liquid fuel such as OMS may be separately fed, metered and brought together in a continuously fashion using a mixing chamber of sufficient but not excessive volume, fitted with an agitator that provides shear-blending of the ingredients.
- the temperature of mixing may be, for example, ambient temperature.
- feeding of the thickening agent into a mixing chamber may be accomplished using an auger conveyor.
- the fluid stream of fuel or other hydrophobic liquid may be fed and metered into the same mixing chamber using a conventional liquid metering pump such as a piston pump.
- the thickened OMS (or other liquid or liquid fuel as discussed herein) may be pumped or otherwise transported from the mixing chamber, for instance, to a holding tank or directly to a filling line where the product is packaged in consumer retail containers.
- the mixed fluid may be passed, for instance, through an intermediate mixing tank to ensure homogeneity, directed into a holding tank, or sent directly to a filling line.
- an appropriately sized container e.g., a 1 pint or a 1 quart or 2 quart capacity container
- a convenient container has sufficiently flexible walls and suitably configured and arranged dispensing hole(s) that allow the fuel composition to be dispensed by squeezing the walls of the container.
- the fuel composition may be dispensed onto charcoal, a wood surface, or any other fuel described herein, e.g., solid fuels.
- thickening agents for hydrocarbon liquids are described, for example, by Cohen, et al. in U.S. Pat. No. 4,012,205. Soaps, waxes, various polymers, sterols and other agents such as fumed silica have been used as thickeners for hydrocarbon liquids.
- gasoline has been thickened and gelled by addition of benzene and polystyrene to form napalm B.
- MGs that are edible, environmentally sustainable, easy to use, and/or inexpensive
- many of the previously described agents have the disadvantages of being either more difficult to utilize, more costly, or employ ingredients that produce greater pollution when burned in air.
- MG molecules may establish an atypical structural array of molecules when compared to their orientation in a classical emulsion.
- MG molecules dispersed in an oil-in-water environment e.g., mayonnaise or vinaigrette dressing
- the glyceryl hydroxyl groups normally face outward into the surrounding aqueous environment, and the fatty acid chains face inward on suspended oil microdroplets.
- the hydroxyl groups and associated glycerine molecules on each MG molecule may form hydrogen bonding bridges linking together neighboring MG molecules in microparticles.
- This hydroxyl bridge configuration would allow the hydrophobic alkane-like fatty acid tails of the MG to extend into the surrounding hydrophobic fuel, enabling these tails to help stabilize this arrangement and thicken the fuel, e.g., alkane molecules.
- MG molecules within groups of MGs or microparticles undergo inversion (with fatty acids facing outward) when heated and dissolved in OMS solvent, and maintain this orientation that provides thickening when precipitated.
- Applicant believes that when pure MGs are heated, melted and then rapidly precipitated while being dispersed in cool OMS, the groups of molecules are unable to flip their original molecular orientation (fatty acids facing inward) and are therefore unable to efficiently thicken a hydrophobic liquid such as OMS. It is also believed that a similar mechanism would be present with other agents discussed herein, e.g., with respect to diglycerides, fatty acids, etc.
- Each OMS composition described above remained immobile and was only minimally absorbed into the surface of these briquettes.
- a second upper layer of 40 briquettes was added and arranged on top of the first layer. In one test, the upper layer of briquettes was oriented flat, and in the second test the briquettes were oriented more or less on edge (i.e., the briquettes' perimeter edge was vertically oriented). No OMS composition was added to this second upper layer of charcoal, so the upper layer remains uncoated. (Contact and transfer of some thickened fluid through contact between the upper and lower layers is not considered coating, and therefore the upper layer remains uncoated following such contact and transfer.)
- This “edge-up” second layer arrangement provided greater air space among the briquettes for increased air circulation during combustion.
- the OMS compositions of this particular example can advantageously remain substantially non-absorbed on the surface of the charcoal or other solid fuel. This condition allows ample time for adding and arranging the above-described upper layer of charcoal on top of the first lower layer of charcoal coated with the OMS composition.
- Other features and advantages present in some embodiments of the invention are as follows: Upon lighting the fuel composition at any point on the bottom layer of charcoal, the fire spread through the entire bed of charcoal. Charcoal briquettes are rapidly and easily ignited using the above-described two layer geometry because heat is beneficially generated and sustained between the lower and upper layers of charcoal.
- the 10-13 minute interval between igniting the thickened OMS fuel and the charcoal being ready for grilling food is approximately one-half the normal time required for lighting charcoal by the conventional method (e.g., spraying unthickened OMS over a compact pre-formed mound of charcoal).
- Applicant also wished to determine whether the use of unmodified fluid OMS could be improved using a method of applying and burning the fuel similar to the new method described above. Accordingly, Applicant repeated the above-described method for igniting two layers of charcoal briquettes, in which the lower layer was soaked with unmodified OMS lighter fluid and the upper layer was not. To the best of Applicant's knowledge, selective application of lighter fluid to a lower layer of charcoal rather than to the upper outer layer runs contrary to commercial instructions. In fact, typical commercial instructions provided with OMS-type charcoal lighter fluids consistently teach the following (paraphrased from several commercial products):
- a thickened hydrophobic biofuel composition was produced using a monomethyl ester fatty acid liquid fuel (methyl decanoate, CAS Reg. No. 110-42-9, product designation CE-1095, P&G Chemicals, Inc., Cincinnati, Ohio).
- This fuel composition was modified by adding and thermo-precipitating a mixture of SFA-MGs (MyverolTM 18-04, described above) and a palm stearin triglyceride (Revel A stearin, Loders Croklaan Inc., Channahon, Ill.). These ingredients were initially heat-solubilized at approximately 70° C. in the CE-1095 liquid as a five-fold concentrate containing approximately 20% by weight MyverolTM 18-04 and approximately 12% Revel A.
- This heated concentrate was then diluted five-fold while being rapidly mixed with CE-1095 provided at ambient temperature to produce a final mixing temperature of 30° C.
- the rapid mixing and accompanying rapid drop in temperature may favor formation of small crystals.
- the final concentration of MG at approximately 4% by weight and the stearin concentration at approximately 2.4% by weight may be used to produce a thick liquid that can remain stationary as a coating, or can flow slowly under mild pressure.
- the resulting fuel composition may, for example, be readily applied and/or be allowed to remain immobilized on a solid fuel, e.g., charcoal or fireplace wood.
- MG and/or other e.g., diglycerides, fatty acids, etc. can be used.
- MyverolTM 18-04 MG concentrations added to fatty acid ester biofuels was between 2% and 8% by weight, while the stearin triglyceride range was between 1% and 4% by weight.
- the combined use (and possible co-crystallization) of MGs with stearin triglycerides may be used in certain fuel compositions discussed herein, e.g., for monoalkyl ester fatty acid biofuels.
- the crystallization of MGs alone may also be used for certain fuel compositions described herein, e.g., as described herein.
- purified glycerine and/or purified saturated fatty acid monoglycerides may be used, although in other embodiments, the glycerine and/or the saturated fatty acid monoglyceride need not be purified.
- the term “purified” used in conjunction with “saturated fatty acid monoglycerides” or SFA-MGs refers to at least one MG agent or substance that has been separated, fractionated, distilled and/or otherwise refined to be substantially free of contaminating chemical and physical substances that interfere with use of these MGs in forming the novel complexes described herein. In this regard, the presence of fatty acid diglyceride substances mixed with fatty acid MGs are not considered contaminating substances.
- a “purified” substance should contain less than 10% by weight of contaminating substances, or less than 5%, 2% or even less than 1% by weight of contaminating substances.
- “purified glycerine” refers to glycerine than is substantially free of contaminating chemical and physical substances that could likewise interfere with the use of glycerine in forming the novel complexes described herein. Purified glycerine should contain less than 10% by weight of contaminating substances, or less than 5%, 2% or even less than 1% by weight of contaminating substances.
- substantially water-free or in the “substantial absence of water” are terms describing mixtures or blends in which at least one purified MG agent and purified glycerine are heated, melted, mixed and cooled together to form a hydrogen-bonded complex, in which any substantial concentration of water can compete, interfere, or block glycerine molecules from forming hydrogen-bonds with the MG molecule. Accordingly, it is preferable that no measurable levels of water are present in the mixture, and that in any event the molar ratio of glycerine molecules to water molecules in the heated mixture should be at least 10:1 and preferably 25:1, 50:1 or 100:1 or even greater.
- substantially pure solid or “purified solid” relates to solid products formed by combining at least one purified SFA-MG and purified glycerine in a mixture that is melted (optionally such that its molecules are able to commingle), cooled and solidified, in which the resulting solids include a hydrogen-bonded G 2 MG molecular complex consisting of two molecules of G hydrogen-bonded to each molecule of MG.
- substantially pure in this regard means that the solids contain less than 10% by weight of contaminating substances, or less than 5%, 2%, or even less than 1% by weight of contaminating substances that could interfere with the thickening of a hydrophobic liquid by the solids.
- a number of contaminating substances may interfere with the stability and use of the present MG agent (or combined MG and diglyceride agent) to thicken a hydrophobic liquid, and may be removed in the process of purification of these agents, at least in certain cases.
- a MG or MG+diglyceride agent is a product of an interesterification reaction and may contain, as contaminants, fatty acids, sodium hydroxide or lipases that hydrolyze and/or interesterify fatty acids with glycerides, these substances can continue to be chemically reactive and can destabilize or interfere with the use of these solids as a thickening agent.
- these contaminating substances may be partially or completely removed during purification in some embodiments of the invention.
- fuel refers to a composition that is freely combustible in air once ignited by a flame source.
- the fuel may be liquid at room temperature and 1 atmosphere, and can be poured and/or pumped. After thickening, the fuel composition can at least partially liquefy during combustion.
- hydrophobic liquid generally refers to a non-aqueous liquid.
- the liquid may, in some embodiments, be a substance that is liquid at room temperature and 1 atmosphere, and that is immiscible with water, i.e., at least a portion of the liquid phase-separates when exposed to water under these conditions.
- hydrophobic liquids include, but are not limited to, alkyd paints and other petroleum solvent-based coatings, fatty acid ester liquids such as methyl esters of C 8 , C 10 , and C 16 , or C 18 fatty acids (e.g., commonly used in consumer products or fuels, e.g., stearic acid).
- saturated fatty acid monoglyceride or SFA-MG refers to a glycerol molecule in which the hydroxyl group on any one or more of the three carbon atoms has been replaced an ester-linked saturated fatty acid such as palmitic acid (C 16:0 ) or stearic acid (C 18:0 ).
- thermo-precipitated refers to an agent such as a MG in which the physical state of the agent is altered from soluble to insoluble via a decrease in the temperature of the fuel.
- a rapid temperature decrease can be used under certain conditions to induce rapid precipitation of a MG, that can be used to thicken a fuel.
- the MG may be easily heated (e.g., to 70° C.) and/or dissolved in a portion, e.g., at least a small portion, e.g., 10% by weight, of the hydrophobic liquid used in the fuel composition.
- the heated and dissolved MG may be rapidly blended, dispersed, and/or cooled with the remaining bulk, e.g., 90% by weight, of the hydrophobic liquid retained at room temperature, which may result in thickening of the fuel composition.
- the monoglyceride agent or MG may precipitate in some embodiments over a temperature range rather than at one specific temperature. In some cases, rapid cooling may assist in precipitating multiple components in a MG agent together.
- SFA-MG saturated fatty acid monoglyceride
- MG monoglyceride
- saturated diglycerides and “trisaturated triglycerides” refer to glycerol molecules in which, respectively, either two or three saturated fatty acid molecules are chemically ester-linked to either two or three of the glycerol's carbon atoms.
- An agent may include, for example, MGs, diglycerides, and/or triglycerides, and/or other components as those discussed herein.
- SFA-MG agent saturated fatty acid monoglyceride agent
- the agent may contain, for example, SFA-MGs, and/or di- and/or tri-glycerides. Other components may also be present in the agent. In some embodiments, a variety of components may be present within the agent that do not excessively interfere with the thickening function of the agent. In some cases in which the agent comprises multiple components, the various components may be combined, e.g., prior to adding and/or thermo-precipitating the agent in the hydrophobic liquid.
- thickened and “thickening” refer to a significant increase in viscosity.
- the viscosity may be increased such that the thickened liquid does not flow as a thin liquid at 20° C.
- the thickening may, for example, result in a fuel having a “syrupy” degree of viscosity or may be thicker, e.g., substantially or fully gelled at 20° C.
- gelled means the thickened material does not appreciably flow when a 2 cm cube is placed on a horizontal surface for 5 minutes at 20° C.
- portion is meant to describe amounts and relative amounts by weight of fuel. More specifically, the term “portion” includes any suitable percentage, including both “small portions” (as little as 1% of an entire amount) and large portions (as much as 100% of an amount).
- a “larger portion” is defined as being at least two-fold greater in weight than a “small portion” or a “smaller portion.” A “larger portion” may also be much greater than two-fold greater than the “smaller portion,” e.g., it may be ten-fold greater, 20-fold greater or even more.
- a smaller portion of one part by weight of a fuel composition containing 60% by weight of dissolved MGs may be diluted by combining with a 19-fold larger portion of cool fuel to produce 20 parts by weight of a combined fuel mixture containing 3% by weight of precipitated MGs that thicken the fuel composition.
- ambient temperature refers to the air temperature in the manufacturing facility that typically ranges from approximately 20° C. to 25° C.
- unheated and essentially unheated are used to describe liquid fuel that is being combined with a heated MG-containing fuel (the latter being typically heated to a temperature of greater than 60° C.).
- the terms refer to liquid fuel that is substantially cooler than the heated fuel. More specifically, these terms are meant to include a broad range of cooler temperatures ranging from refrigerated temperatures (that may be as low as 0° C.) to temperatures as high as 40° C.
- refrigerated temperatures that may be as low as 0° C.
- temperatures high as 40° C.
- unheated and essentially unheated temperatures are often at ambient temperatures, typically in the range of 20-25° C.
- the term “charcoal” refers to charcoal in relatively large chunks, e.g., either or both irregular or unshaped lump charcoal and shaped briquette-style charcoal. Unless unshaped lump charcoal is specifically excluded, use of the term “charcoal briquettes” may include both shaped briquettes and the unshaped lump charcoal. Similarly, unless shaped briquette charcoal is specifically excluded, use of the term “lump charcoal” includes both shaped briquettes and the unshaped lump charcoal.
- ash-covered refers to a bed of charcoal whose exposed surface is at least 50% covered with ash produced by the ignited surface.
- the phrase and terms contained herein for methods of lighting charcoal describe “applying the fuel composition to a first lower layer of charcoal resting on a non-combustible support grate in a barbecue grill.”
- This phrase refers to either a thickened or unthickened hydrocarbon or alkyl ester-based hydrophobic fuel that is sprayed or otherwise dispensed onto the exposed upward-facing surfaces of a layer of charcoal briquettes or lumps placed side-by-side on a typical metal grate that supports charcoal in a grill.
- This initial layer of charcoal constituting the so-called “first lower layer” is distinguished from the “second upper layer” of charcoal (in most cases an amount roughly similar to the first lower layer).
- the second upper layer is placed on top of the first lower layer, and does not necessarily require addition of any more lighter fuel.
- the charcoal “support grate” must allow ample air circulation around the charcoal to support combustion.
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Abstract
Description
-
- (a) reducing contamination of the hands and the outside of the storage container by OMS liquid;
- (b) allowing more uniform application of OMS onto briquettes and irregular lumps of charcoal owing to the visibility of the thickened white coating;
- (c) reducing the absorption of OMS into the charcoal allowing easier ignition of surface fuel for a longer time interval following application, and earlier volatilization of undesirable OMS odors from ignited charcoal; and
- (d) more efficient ignition of briquettes allowing less fluid to be used per fire.
-
- Lighting instructions: Arrange charcoal briquettes in a pile or pyramid. Apply starter fluid over the pile of charcoal, use 1.6 fluid ounces (47 milliliters) per pound of charcoal. Light the charcoal immediately. The starter fluid will burn off cleanly in a few minutes leaving the charcoal fully ignited. When briquettes ash over, spread them out evenly and begin barbecuing.
Claims (19)
Priority Applications (1)
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US13/467,863 US8535398B1 (en) | 2012-05-09 | 2012-05-09 | Chemical complexes comprising glycerine and monoglycerides for thickening purposes |
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Application Number | Priority Date | Filing Date | Title |
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US13/467,863 US8535398B1 (en) | 2012-05-09 | 2012-05-09 | Chemical complexes comprising glycerine and monoglycerides for thickening purposes |
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US8535398B1 true US8535398B1 (en) | 2013-09-17 |
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US13/467,863 Expired - Fee Related US8535398B1 (en) | 2012-05-09 | 2012-05-09 | Chemical complexes comprising glycerine and monoglycerides for thickening purposes |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104774658A (en) * | 2015-03-10 | 2015-07-15 | 重庆思派恩环保科技有限公司 | Solid fuel additive |
CN108138065A (en) * | 2015-08-31 | 2018-06-08 | 弗劳恩霍夫应用研究促进协会 | Lubrication mixture with glyceride |
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CN108138065A (en) * | 2015-08-31 | 2018-06-08 | 弗劳恩霍夫应用研究促进协会 | Lubrication mixture with glyceride |
CN108138065B (en) * | 2015-08-31 | 2021-01-12 | 弗劳恩霍夫应用研究促进协会 | Lubricating mixture with glycerides |
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